Impact of Bi³⁺ Heterovalent Doping in Organic–Inorganic Metal Halide Perovskite Crystals

Intrinsic organic–inorganic metal halide perovskites (OIHP) based semiconductors have shown wide applications in optoelectronic devices. There have been several attempts to incorporate heterovalent metal (e.g., Bi 3+ ) ions in the perovskites in an attempt to induce electronic doping and increase the charge carrier density in the semiconductor. It has been reported that inclusion of Bi 3+ decreases the band gap of the material considerably. However, contrary to the earlier conclusions, despite a clear change in the appearance of the crystal as observed by eye, here we show that the band gap of MAPbBr 3 crystals does not change due the presence of Bi 3+ in the growth solution. An increased density of states in the band gap and use of very thick samples for transmission measurements, erroneously give the impression of a band gap shift. These sub band gap states also act as nonradiative recombination centers in the crystals.